9-and 10-hydroxyoctadecylamines



United States 9- AND IO-HYDRQXYGCTADECYLANHNES No Drawing. ApplicationFebruary 18, 1950,

Serial No. 145,088

1 Claim. (31. 260584) This invention relates to the preparation ofhydroxyamines. The invention is particularly useful in the production ofahydroxyamine having 18 carbon atoms, and in which there is anoxygen-linked ester radical attached to the ninth or tenth carbon atom.The hydroxyamines are useful in forming wax-like compounds andquaternary ammonium compounds.

An object of the invention is to produce as a new productmono-hydroxyamines and a process for preparing the same. Other specificobjects and advantages will appear as the specification proceeds.

We have discovered that by employing a critical range of temperatures ahydroxy nitrile of high molecular weight may be effectively hydrogenatedso as to produce mono-hydroxyamines in excellent yield and quality.

The usual range of temperatures employed in the hydrogenation ofnitriles, etc., is about l-l20 C. at 50-300 lbs. pressure. Sometimeshigher temperatures may be reached before decomposition occurs. We havediscovered that there is a higher and critical range that must beemployed for the effective hydrogenation of the hydroxy nitriles, andthis range is approximately 14 200 C. The minimum temperature is 150 C.at the same pressure at which ordinary nitriles may be hydrogenated at100 C. However, We can reduce the temperature to 140 C. by using about1400 pounds pressure. In the carrying out of the present invention weprefer to employ temperatures of from 140 C. to 200 C., and pressures ofapproximately 150 to 2,000 pounds.

We prefer to use as a starting material a hydroxy nitrile having 18carbon atoms and having a hydroxyl or an oxygen-linked ester radicalattached to the ninth or tenth carbon atom. This may be produced in anysuitable manner.

in the co-pending application of Robert J. Vander Wal, Serial No.792,353, now Patent No. 2,558,666, for Nitrile Derivatives, there areset out a number of hydroxy nitriles, together with various methods forproducing these. For example, as a starting material We may use theproducts described in said application as an uninterrupted straightchain aliphatic nitrile of at least 18 carbon atoms, selected from thegroup consisting of where R is an aliphatic hydrocarbon radical.

Specific hydroxy nitriles, as enumerated in the above application, maybe 9-hydroxy stearonitrile, IO-hydroxy stearonitrile, the acetic acidester of 9-hydroxy stearonitrile or lO-hydroxystearonitrile, the oleoylester of 9-hydroxy stearonitrile or -hydroxy stearonitrile.

Starting with a hydroxy nitrile as above described, we

atenr l ice find that this may be effectively reduced to the amine byhydrogenation in the presence of a hydrogenation catalytic agent whenthe temperatures are maintained within the critical range of l-200 C.,and with corresponding pressures ranging between 150 pounds to 2,000pounds. The hydroxyamine product has been found useful for forming awax-like compound, and also for forming a quaternary ammonium compound,etc.

The following specific exarnples must be set out:

Example I 160 parts of a mixture of 9 and 10 hydroxystearonitriles,prepared from red oil nitriles according to the procedure outlined inco-pending application No. 536,617, now abandoned, and distilled,together with 3.2 parts of Raney nickel catalyst and 3.2 parts of 5%sodium hydroxide solution, were subjected to a pressure of 1400 poundsper square inch and a temperature of 140 C. for 4 /2 hours. The catalystwas removed by filtration and the product was distilled yielding 91.7parts of a mixture of 9 and 10 hydroxyocetadecylamine having a boilingpoint of 173l80 C. at 0.35 mm. The residue consisted of 58.5 parts of amixture of 9 and 10 dihydroxydioctadecylamine which melted at 82-83 C.after crystallization from alcohol.

Example II l grams of hydroxystearonitrile, 6 grams of Raney nickelcatalyst [50% Ni in water], 3 ml. 5% NaOH were placed in the Parrpressure reaction apparatus. The apparatus was blown twice with poundsof hydrogen to sweep out the air contained therein.

The hydrogenation was carried predominantly at pressures not exceeding150 p. s. i. and at temperatures ranging from to C. with rapidagitation. During the first 48 minutes, a drop in hydrogen pressure of70 p. s. i. was observed. A drop of 65 p. s. i. was observed during thenext 80 minutes and of 80 p. s. i. during the subsequent minutes. Thehydrogen absorbed during the last 60 of the aforementioned 190 minuteswas negligible, amounting to a drop of less than 5 p. s. i., showingthat the reaction had definitely slowed down if not stopped altogetherat the low pressure employed. In order to finish the reduction thehydrogen pressure was increased to 300 p. s. i. and again to 500 p. s.i.

Total hydrogen absorbed at pressure less than 150 p. s. i. wasrepresented by a drop in pressure of 232 p. s. i.

Total hydrogen absorbed at hi her pressures of 300 to 500 p. s. i. wasrepresented by a drop in pressure of 75 p. s. 1.

The reduction time at the lower pressures was 5 hours and 20 minutes,while at the higher pressures was 3 hours.

The reduced product was removed from the bomb, filtered to remove thesuspended catalyst and distilled under reduced pressure.

136.3 grams distilled.

Distillate=87.6 grams, B. P. l70l85 at 0.5 mm., 64.5%.

Residue-=44.5 grams, 32.6%. N. E. of distillate=305.

Example IIIEsteramide wax A one mole quantity of hydroxyoctadecylaminewas mixed with a two molar quantity of stearic acid. The mixture washeated slowly up to 250-260 C. Water evolved and was removed. Theproduct cooled to a soft, waxy solid which melted at 40 50 C. Analysisshowed 13% free fatty acid. The main product was an esteramide.

Example I V.N .N-dimethyllzyrlroxyocmdecy[amine To a mixture of 21.7 g.of 9-hydroxyoctadecylamine,

a 11 ml. of H and 3.2 ml. of alcohol, was slowly added 13 ml. of 85%formic acid. The mixture was stirred during the addition and thetemperature was not allowed to rise above 80 C. After cooling, 20 ml. of36% formaldehyde was added and the reaction Wasallowed to proceed at6080 C. The time required was about two hours. When the evolution ofcarbon dioxide stopped, the solution was made alkaline with sodiumhydroxide and the amine separated and dried .over sodium carbonate.

Example V.-Trimethylhydroxyoctadecy[ammonium chloride T o grams ofdimethylhydroxyoctadecylamine'cooled to C. was added a cooled solutionof 10 grams of to room temperature and opened. The excess methyl ExampleVI.Acet0xy0ctadecylamine A mixture of grams of acetoxyoctadecanenitrile,

The methanol was i 1 cc. of 5% sodium hydroxide and 2 grams of 50% Raneynickel was placed in a bomb and hydrogenated at 140 C. and 2000 p. s. i.pressure. In 2 hours there was a pressure drop of 200 p. s. i. The bombwas cooled to C. and the contentswere filtered to remove the catalyst.The acetoxyoctadecylamine was distilled; B. P. 'l60l7.0 C./ 1.0 mm. Theneutral equivalent Was found to be 330; the theoretical for thiscompound is 327.

While in the foregoing specification we have set out the process stepsin considerable detail, it will be understood that such details may bevaried by those skilled in the art without departing from the spirit ofour invention.

We claim:

A mixture of 9-l1ydroxyoctadecylamine with 10-hydroxyoctadecylamine.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Carter et al.: J. Biological Chem, 170, pages 295-9..

